Synthesis and characterization of new metal carbon catalysts for hydrogenation of d glucose

SYNTHESIS AND CHARACTERIZATION OF NEW METAL-CARBON CATALYSTS FOR HYDROGENATION OF D-GLUCOSE LIU JIAJIA NATIONAL UNIVERSITY OF SINGAPORE 2010 SYNTHESIS AND CHARACTERIZATION OF NEW METAL-CARBON CATALYSTS FOR HYDROGENATION OF D-GLUCOSE LIU JIAJIA (M.Eng, Tianjin University) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMICAL AND BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2010 Acknowledgement Acknowledgement I am heartily thankful to my supervisor, Assoc. Prof. Zhao X. S., George, whose constant encouragement, invaluable guidance, patience and support throughout the whole period of my PhD candidature. I would also like to thank Assoc. Prof. Zhao for his guidance on writing scientific papers including this PhD thesis. In addition, I want to express my sincerest appreciation to the Department of Chemical and Biomolecular Engineering for offering me the chance to study at NUS with a scholarship. It’s my pleasure to work with a group of brilliant, warmhearted and lovely people. Wish all my lab mates go well with their work. Particular acknowledgement goes to Dr. Liu Tao, Mr. Chia Phai Ann, Mr. Shang Zhenhua, Dr. Yuan Zeliang, Mr. Mao Ning, Mr. Liu Zhicheng, Dr. Rajarathnam D., Madam Chow Pek Jaslyn, Mdm Fam Hwee Koong Samantha, Ms Lee Chai Keng, Ms Tay Choon Yen, Mr. Toh Keng Chee, Mr. Chun See Chong, Ms. Ng Ai Mei, Ms. Lum Mei Peng Sharon, and Ms. How Yoke Leng Doris for their kind supports. I thank my parents and my husband. It is no exaggeration to say that I could not complete the PhD work without their generous help, boundless love, encouragement and support. Lastly, I offer my regards and blessing to all of those who supported me in any respect during the completion of the project. i Table of Contents Table of Contents Acknowledgement i Table of Contents ii Summary . v Nomenclature . viii List of Tables ix List of Figures . x Chapter 1. Introduction 1.1 Hydrogenation reactions . 1.2 Importance of hydrogenation of D-glucose 1.3 Catalysts for hydrogenation reactions . 1.4 Carbon-supprted catalysts for hydrogenation reactions 1.5 Recent advance on template approach to preparing novel porous carbons and catalysts . 1.6 Objective of project . 1.7 Structure of thesis . Chapter 2. Literature review 11 2.1 Hydrogenation reactions . 11 2.2 Catalysts in hydrogenation reactions 13 2.3 Hydrogenation of D-glucose . 37 2.4 Porous carbon as a catalyst support 43 Chapter 3. Experimental section 59 3.1 Chemicals 59 3.2 Synthesis methods . 60 ii Table of Contents 3.3 Characterization techniques 63 3.4 Evaluation of catalytic properties . 75 Chapter 4. Ru nanoparticles embedded in templated porous carbon and catalytic performance in D-glucose hydrogenation . 77 4.1 Introduction . 77 4.2 Characterization of Ru nanoparticles catalysts . 77 4.3 Catalytic properties . 84 4.4 Summary . 91 Chapter 5. Bimetallic Ru-Cu nanoparticles sandwiched in porous carbon . 92 5.1 Introduction . 92 5.2 Characterization of bimetallic Ru-Cu catalysts 94 5.3 Catalytic properties . 106 5.4 Summary . 108 Chapter 6. Ruthenium nanoparticles embedded in mesoporous carbon fibers . 109 6.1 Introduction . 109 6.2 Characterization of Ru nanoparticles catalysts . 111 6.3 Catalytic properties . 122 6.4 Summary . 126 Chapter 7. Kinetics of the catalytic hydrogenation of D-glucose over bimetallic RuCu carbon catalyst . 127 7.1 Introduction . 127 7.2 Kinetics of the hydrogenation of D-glucose . 128 7.3 Modeling results of kinetics and mechanism 132 7.4 Summary . 135 Chapter 8. Conclusions and recommendations . 137 iii Table of Contents 8.1 Conclusions . 137 8.2 Recommendations . 139 References . 140 Appendix . 162 iv Summary Summary Catalytic hydrogenation is a process for the reduction of chemical substances, and has found numerous applications in the chemical and petrochemical industries. The hydrogenation reaction can be carried out heterogeneously or homogeneously. The heterogeneous catalysts are in generally a metal supported on a solid that are prepared by using conventional methods, such as impregnation followed by hydrogen reduction. Such supported catalysts suffer from a number of problems, such as aggregation and leaching of the metal particles. Thus, new methods that afford the preparation of catalytically highly active, chemically and thermally stable, technically reusable, and cost-effective are highly desirable. In this thesis work, the template strategy was employed to prepare new heterogeneous catalysts. The catalysts were characterized using a number of techniques, such as extended X-ray absorption spectroscopy (XAS) and chemisorption of hydrogen and carbon monoxide. The catalytic properties of the catalysts were evaluated using the hydrogenation of D-glucose in a batch reactor. First, ruthenium nanoparticles embedded in the pore walls of templated carbon (denoted RuC) were prepared by using H-form zeolite Y and mesoporous silica SBA15 as templates. Compared with other ruthenium catalysts prepared using conventional methods, the RuC catalysts prepared using the template method exhibited a significantly improved catalytic performance because of the unique structure of the RuC catalysts. Second, bimetallic ruthenium-copper (Ru-Cu) nanoparticles embedded in the pore walls of mesoporous carbon were prepared. The presence of bimetallic entities was supported by the characterization data of both Ru LIII-edge and Cu K-edge X-ray v Summary absorption. It was observed that additional active sites were created because of the spillover of H from Ru to Cu at low Cu contents while three-dimensional islands of segregated metallic Cu phase covering the surface of Ru nanoparticles appeared at high Cu contents. Third, alumina microfibers were also used as templates to prepare Ru nanoparticles embedded in mesoporous carbon fibers. In comparison with Ru nanoparticles supported on other carbon materials (e.g., multi-walled carbon nanotubes, carbon fibers, alumina microfibers, and the activated charcoals), the Ru catalyst prepared using the template method displayed a remarkably higher catalytic activity and a better stability, again attributed to the features of unblocked mesopores, hydrogen spillover, and unique surface contact between the Ru nanoparticles and the carbon supports. In addition, the incorporation of nitrogen significantly improved the catalytic performance due to the enhanced hydrogen adsorption, improved surface wettability, and modified electronic properties of the Ru nanoparticles. Fourth, the kinetics of D-glucose hydrogenation over a bimetallic catalyst was studied. In the operation regime studied, the reaction rate showed a first order dependency with respect to hydrogen. The rate dependence on D-glucose was found to be concentration-dependent: at low D-glucose concentrations the reaction rate showed a first order dependency while at higher concentrations a zero order behavior was observed. Experimental data were fitted to the kinetic model using the Matlab software with the fminsearch method. The kinetic model was found to nicely predict the experimental data. In short, the template method offers opportunities to prepare novel solid catalysts with unique properties, such as controllable catalyst particle size, enhanced catalyst dispersion, improved thermal stability, lowered diffusion resistance of both reagent vi Summary and product, and intimate interfacial contact between metal particles and the carbon support. In addition, the template method could be extended to the preparation of bimetallic or tri-metallic carbon nanocomposites. 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Carbon, 45, pp.1111-1113. 2007. 161 Appendix APPENDIX List of publications coming from this thesis work Papers published (or accepted) in international referred journal and book (1) Liu, J., Zhao, X.S. Glucose Hydrogenation over Ru Nanoparticles Embedded in Template Porous Carbon. Studies in Surface Science and Catalysis, 2008, 174, 13151318. (2) Liu, J., Tian, X.N., and Zhao, X. S. Hydrogenation of Glucose over Ru Nanoparticles Embedded in Templated Porous Carbon. Australian Journal of Chemistry, 2009, 62, 1020-1026. (3) Su, F., Lee F. Y., Lv, L., Liu, J., Tian, X.N., and Zhao, X.S. Sandwiched Ruthenium/Carbon Nanostructures for Highly Active Heterogeneous Hydrogenation. Advanced Functional Materials, 2007, 17, 1926-1931. (4) Su, F., Zhou, Z., Guo, W., Liu, J., Tian X.N., and Zhao, X.S. Template Approaches to Synthesis of Porous Carbon. in Chemistry and Physics of Carbon, Vol. 30, pp. 63128, Ed: L. R. Radovic, CRC Press, 2008. (5) Liu, J., Zhao, X.S. Ru Nanoparticles Embedded in Templated Carbon Pore Walls as a Highly Active Catalyst for Glucose Hydrogenation. Accepted by 14th International Congress on Catalysis. 2008, Seoul, Korea. (6) Zhao, X.S., Su, F., and Liu, J. Metal Nanoparticles Embedded in Porous Carbon as a New Catalyst System (keynote). Accepted by XIX International Materials Research Congress, 2010, Cancún, Mexico. (7) Liu, J., Zhao, X.S. Ruthenium Nanoparticles Embedded in Carbon Microfibers as a Catalyst for Glucose Hydrogenation. Accepted by The 6th Tokyo Conference on Advanced Catalytic Science and Technology & 5th Asia-Pacific Congress on Catalysis (TOCAT6/APCAT5), 2010, Sapporo, Japan. Papers submitted to international referred journal (8) Liu, J., Zhang, L.L., Liu, T. and Zhao, X.S. Bimetallic Ruthenium-Copper Nanoparticles embedded in Porous Carbon for Hydrogenation of D-glucose. To be submit to ACS catalysis, 2010. (9) Liu, J., Bai, P. and Zhao, X.S. Template Approach to the Synthesis of Mesoporous Carbon Microfiber Supported Ruthenium Catalyst for the Hydrogenation of D-glucose. To be submit to Physical Chemistry Chemical Physics, 2010. 162 [...]... ketones; ii) hydrogenation of unsaturated aldehydes; iii) hydrogenation of aromatic aldehydes and ketones; iv) sugar hydrogenation; v) enantioselective carbonyl hydrogenation; vi) hydrogenation of esters, anhydrides and carboxylic acids The rates of hydrogenation of carbonyl compounds depend on the nature of catalyst, the structure of compounds, such as aliphatic or aromatic and hindered or unhindered, the... facilitated the addition of hydrogen to molecules of hydrocarbon compounds Since then catalytic hydrogenation has been widely used in various fields Important examples of industrial hydrogenation processes are the synthesis of methanol, liquid fuels, hydrogenated oils, cyclohexanol and cyclohexane In the food industry, hydrogenation is applied to process vegetable oils and fats (Patterson, 1983) Triglycerides... preferred for special applications (Molnar et al., 2001) 2.1.2 Hydrogenation of C=O bonds Hydrogenation of carbonyl groups occurs readily over most catalysts However, hydrogenolysis of the resulting hydroxyl group and further reduced to methylene group must be careful to be prevented The hydrogenation of carbonyl groups can be summarized to a few reaction types: i) hydrogenation of aliphatic aldehydes and. .. used to prepare hydrogenation catalysts A systematic comparative study of preparing catalysts via gas phase deposition and via wet impregnation and testing in cinnamaldehyde hydrogenation was performed by Lashdaf et al (2003) Small Pd metal crystallites were formed by gas-phase deposition method even with high metal loadings, whereas larger Pd particles were achieved via impregnation Additionally, Pd... they resided on the surface sufficiently long enough to allow side reactions to occur Catalytic hydrogenation of nitriles may result in several products: primary, secondary, and tertiary amines; imines; hydrocarbons; aldehydes; amides; and alcohols The main product depends on the nature of catalyst, structure of substrate, basic and acidic additives, the reaction medium and other reaction conditions... catalytic performances of the RuC catalysts were compared with other Ru-C catalysts prepared by conventional method Chapter 5 describes the fabrication of bimetallic Ru-Cu nanoparticles embedded in the pore walls of mesoporous carbon The presence of bimetallic entities was characterized and the bimetallic catalysts were evaluated in D- glucose hydrogenation Chapter 6 is the details of synthesis of the mesoporous... kinds of fatty acid combined in any one triglyceride will determine the chemical and physical nature of the fat Unsaturated vegetable fats and oils can be hydrogenated by the catalytic addition of hydrogen at the ethylenic linkages of their acids to produce saturated or partially saturated fats and oils of higher melting point The most common forms are shortening, margarines, and the partially hydrogenated... SiO2 supported) catalysts Promoters typically enhance the activity and selectivity of both precious and base 12 Chapter 2 Literature Review metal catalysts for carbonyl reductions where the types and amounts of promoters need to be optimized for the desired reaction 2.1.3 Hydrogenation of nitrogen-containing multiple bonds The metal catalyzed hydrogenation of nitro-, nitroso-, azo-, and nitrile-groups... industrial application of hydrogenation of carbon- carbon multiple bonds The classical heterogeneous catalysts for carbon- carbon multiple bond hydrogenations involve supported precious metals, activated base metal catalysts (such as Raney-Ni) and nickel supported on oxides For fine chemicals 11 Chapter 2 Literature Review manufacture activated carbon is the most common support material Aluminas and. .. types of catalysts, homogeneous catalysts and heterogeneous catalysts The 3 Chapter 1 Introduction homogeneous catalysts are metal complexes that are soluble in the reaction medium Such metal complexes consist of a central metal ion and organic ligands The activity and selectivity of homogeneous catalysts are adjusted by changing the ligands The catalytic cycle starts with oxidative additive of an . SYNTHESIS AND CHARACTERIZATION OF NEW METAL- CARBON CATALYSTS FOR HYDROGENATION OF D- GLUCOSE LIU JIAJIA (M.Eng, Tianjin University) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR. SYNTHESIS AND CHARACTERIZATION OF NEW METAL- CARBON CATALYSTS FOR HYDROGENATION OF D- GLUCOSE LIU JIAJIA NATIONAL UNIVERSITY OF SINGAPORE 2010 SYNTHESIS. reactions 1 1.2 Importance of hydrogenation of D- glucose 3 1.3 Catalysts for hydrogenation reactions 3 1.4 Carbon- supprted catalysts for hydrogenation reactions 6 1.5 Recent advance on template approach